Modified ion exchange resin for removing impurity metal ions in plating solution and preparation method of modified ion exchange resin

Abstract

The invention relates to the technical field of electroplating materials, and particularly discloses modified ion exchange resin for removing impurity metal ions in a plating solution and a preparation method of the modified ion exchange resin. The preparation method of the modified ion exchange resin for removing the impurity metal ions in the plating solution comprises the following steps: an amination reaction step: mixing ion exchange resin with a diamine compound, adding a solvent, uniformly stirring, and carrying out a stirring reaction at 40-60 DEG C for 4-6 h to obtain the aminated ion exchange resin; a cross-linking reaction step: adding the aminated ion exchange resin into a formaldehyde aqueous solution, adjusting the pH value to 7-9, and stirring and reacting at 50-70 DEG C for 4-6 hours to obtain cross-linked ion exchange resin; and taking the cross-linked ion exchange resin to obtain the modified ion exchange resin for removing the impurity metal ions in the plating solution. Researches show that the removal capacity of the modified ion exchange resin prepared by the brand new method to copper ions in water is greatly higher than that of unmodified ion exchange resin; the excellent copper ion removal capability is realized.

Description

Technical Field

[0001] The invention relates to the technical field of electroplating materials, and in particular to a modified ion exchange resin for removing impure metal ions in a plating solution and a preparation method thereof. Background Art

[0002] Electroplating, a surface treatment technology that can be used to decorate, protect, and provide functional effects on metal and non-metal surfaces, has become an indispensable supporting industry in my country's manufacturing industry. It is widely used in machinery, instrumentation, light industry, printed circuit boards, electronic components, aerospace, and other fields. However, for a long time, the extensive operations of my country's traditional electroplating industry have not only polluted the environment, but also led to low business profitability and difficulties in sustainable development. Impure metal ions in electroplating wastewater and plated component cleaning wastewater not only seriously harm the environment but also cause problems such as low production efficiency and poor product quality in electroplating production lines. Furthermore, impure metal ions in the plating solution also affect the physicochemical properties of the plating solution, altering its electrochemical characteristics, affecting the uniformity and crystallization quality of the coating, resulting in numerous coating defects and poor interfacial bonding, ultimately affecting properties such as gloss, hardness, and corrosion resistance.

[0003] Ion exchange resins are polymer materials with ion exchange capabilities, and cation exchange resins are commonly used to remove impure metal ions from electroplating wastewater. Due to the wide variety of impure metal ions, existing cation exchange resins, while effective at removing these ions, lack specificity. For example, when the concentration of a particular ion in the electroplating solution is very high, their ability to treat a particular metal ion is limited. Therefore, providing a series of modified ion exchange resins with varying treatment effects for different metal ions can provide those skilled in the art with targeted options based on the metal ions they need to treat in electroplating wastewater, thus offering significant application value. Summary of the Invention

[0004] In order to overcome at least one of the technical problems existing in the prior art, the present invention first provides a modified ion exchange resin for removing impurity metal ions in a plating solution and a preparation method thereof.

[0005] The technical solutions of the present invention are as follows:

[0006] A method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution, characterized by comprising the following steps:

[0007] Amination reaction step: taking an ion exchange resin and a diamine compound, mixing them, adding a solvent and stirring them evenly, stirring and reacting them at 40-60° C. for 4-6 hours to obtain an aminated ion exchange resin;

[0008] The cross-linking reaction step comprises adding an aminated ion exchange resin to a formaldehyde aqueous solution, adjusting the pH value to 7 to 9, and stirring the reaction at 50 to 70° C. for 4 to 6 hours to obtain a cross-linked ion exchange resin; and taking the cross-linked ion exchange resin to obtain the modified ion exchange resin for removing impurity metal ions in the plating solution.

[0009] The present invention provides a novel method for preparing a modified ion exchange resin. Studies have shown that the modified ion exchange resin prepared by the novel method has a significantly higher ability to remove copper ions from water than unmodified ion exchange resin.

[0010] Preferably, in the amination reaction step, the weight ratio of the ion exchange resin to the diamine compound is 10:2-4.

[0011] Preferably, in the amination reaction step, the weight ratio of the ion exchange resin to the diamine compound is 10:3.

[0012] Preferably, the diamine compound is selected from undecanediamine or p-phenylenediamine.

[0013] Preferably, the diamine compound is selected from a combination of undecanediamine and p-phenylenediamine.

[0014] Preferably, the weight ratio of undecanediamine to p-phenylenediamine is 4-6:1-3.

[0015] Most preferably, the weight ratio of undecanediamine to p-phenylenediamine is 5:2.

[0016] The inventors discovered in further research that the selection of diamine compounds is crucial in the preparation of the modified ion exchange resin of the present invention. A modified ion exchange resin prepared from a diamine compound composed of undecanediamine and p-phenylenediamine exhibits significantly higher copper ion removal capabilities than a modified ion exchange resin prepared from either undecanediamine or p-phenylenediamine alone.

[0017] The modified ion exchange resin prepared from a diamine compound composed of undecanediamine and p-phenylenediamine can synergistically improve the removal ability of the modified ion exchange resin for copper ions; thus, the prepared modified ion exchange resin has very excellent removal ability for copper ions.

[0018] Preferably, the solvent in the amination reaction step is methanol.

[0019] Preferably, in the cross-linking reaction step, the ratio of the amount of the aminated ion exchange resin to the formaldehyde aqueous solution is 1 kg: 3-5 L.

[0020] Preferably, in the cross-linking reaction step, the ratio of the amount of the aminated ion exchange resin to the formaldehyde aqueous solution is 1 kg:4 L.

[0021] Preferably, the mass fraction of formaldehyde in the formaldehyde aqueous solution is 35-40%.

[0022] Preferably, the mass fraction of formaldehyde in the formaldehyde aqueous solution is 37%.

[0023] Preferably, the impurity metal ions are copper ions.

[0024] Preferably, the ion exchange resin is D001 macroporous adsorption resin.

[0025] The present invention also provides a modified ion exchange resin prepared by the above preparation method for removing impurity metal ions in the plating solution.

[0026] Beneficial Effects: This invention provides a novel method for preparing a modified ion exchange resin. Studies have shown that the modified ion exchange resin prepared using this novel method significantly improves copper ion removal from water compared to unmodified ion exchange resins, demonstrating excellent copper ion removal capabilities. When treating electroplating wastewater containing high concentrations of copper ions, the modified ion exchange resin prepared using this method demonstrates superior removal capabilities and possesses significant application value. DETAILED DESCRIPTION

[0027] The present invention is further explained below with reference to specific examples, but the examples do not limit the present invention in any form.

[0028] Example 1 Preparation Method of Modified Ion Exchange Resin for Removing Metal Ions from Plating Solutions

[0029] (1) Amination reaction step: taking an ion exchange resin and a diamine compound, mixing them, adding methanol and stirring evenly, stirring and reacting at 50° C. for 5 hours, washing with deionized water after the reaction to remove unreacted amine compound, and obtaining an aminated ion exchange resin; wherein the weight ratio of the ion exchange resin to the diamine compound is 10:3; the ion exchange resin is a D001 macroporous adsorption resin; and the diamine compound is undecanediamine;

[0030] (2) Cross-linking reaction step: adding an aminated ion exchange resin to a formaldehyde aqueous solution, adjusting the pH value to 8, stirring and reacting at 60° C. for 5 hours, washing with deionized water after the reaction to remove unreacted formaldehyde, and obtaining a cross-linked ion exchange resin; taking the cross-linked ion exchange resin to obtain the modified ion exchange resin for removing impurity metal ions in the plating solution; wherein the amount ratio of the aminated ion exchange resin to the formaldehyde aqueous solution is 1 kg:4 L; the mass fraction of formaldehyde in the formaldehyde aqueous solution is 37%.

[0031] Example 2 Preparation Method of Modified Ion Exchange Resin for Removing Metal Ion Impurities from Plating Solution

[0032] (1) Amination reaction step: taking an ion exchange resin and a diamine compound, mixing them, adding methanol and stirring evenly, stirring and reacting at 50° C. for 5 hours, washing with deionized water after the reaction to remove unreacted amine compound, and obtaining an aminated ion exchange resin; wherein the weight ratio of the ion exchange resin to the diamine compound is 10:3; the ion exchange resin is a D001 macroporous adsorption resin; and the diamine compound is p-phenylenediamine;

[0033] (2) Cross-linking reaction step: adding an aminated ion exchange resin to a formaldehyde aqueous solution, adjusting the pH value to 8, stirring and reacting at 60° C. for 5 hours, washing with deionized water after the reaction to remove unreacted formaldehyde, and obtaining a cross-linked ion exchange resin; taking the cross-linked ion exchange resin to obtain the modified ion exchange resin for removing impurity metal ions in the plating solution; wherein the amount ratio of the aminated ion exchange resin to the formaldehyde aqueous solution is 1 kg:4 L; the mass fraction of formaldehyde in the formaldehyde aqueous solution is 37%.

[0034] Example 3 Preparation Method of Modified Ion Exchange Resin for Removing Metal Ion Impurities from Plating Solution

[0035] (1) Amination reaction step: taking an ion exchange resin and a diamine compound, mixing them, adding methanol and stirring evenly, stirring and reacting at 50° C. for 5 hours, washing with deionized water after the reaction to remove unreacted amine compound, and obtaining an aminated ion exchange resin; wherein the weight ratio of the ion exchange resin to the diamine compound is 10:3; the ion exchange resin is a D001 type macroporous adsorption resin; and the diamine compound is composed of undecanediamine and p-phenylenediamine in a weight ratio of 5:2;

[0036] (2) Cross-linking reaction step: adding an aminated ion exchange resin to a formaldehyde aqueous solution, adjusting the pH value to 8, stirring and reacting at 60° C. for 5 hours, washing with deionized water after the reaction to remove unreacted formaldehyde, and obtaining a cross-linked ion exchange resin; taking the cross-linked ion exchange resin to obtain the modified ion exchange resin for removing impurity metal ions in the plating solution; wherein the amount ratio of the aminated ion exchange resin to the formaldehyde aqueous solution is 1 kg:4 L; the mass fraction of formaldehyde in the formaldehyde aqueous solution is 37%.

[0037] Experimental Example 1 Copper ion removal ability test

[0038] Copper sulfate was added to water to prepare a high-concentration copper ion aqueous solution with a copper ion content of 500 mg / L; the high-concentration copper ion aqueous solution was then passed through an ion exchange resin column containing the ion exchange resin to be tested at a high flow rate of 5 BV / L; the effluent after passing through the ion exchange resin column was collected, and the copper ion content in the effluent was detected; the results are shown in Table 1.

[0039] The ion exchange resin to be tested used in the experimental group was the modified ion exchange resin prepared in Examples 1 to 3 for removing impurity metal ions in the plating solution; the ion exchange resin to be tested used in the control group was a D001 macroporous adsorption resin.

[0040] Table 1. Copper ion removal ability test results

[0041]

[0042]

[0043] As can be seen from the experimental results in Table 1, the copper ion content in the effluent of experimental groups 1 and 2 is significantly lower than that of the control group; this indicates that the modified ion exchange resin prepared by the novel method of the present invention has a significantly higher ability to remove high-concentration copper ions in water at a high speed than the unmodified D001 macroporous adsorption resin.

[0044] As can be seen from the experimental results in Table 1, the copper ion content in the effluent of Experimental Group 2 was 0.2 mg / L, demonstrating excellent copper ion removal capacity, significantly lower than that of Experimental Groups 1 and 2. This demonstrates that the selection of diamine compounds is crucial; the modified ion exchange resin prepared from a diamine compound composed of undecanediamine and p-phenylenediamine exhibits significantly higher copper ion removal capacity than modified ion exchange resins prepared from either undecanediamine or p-phenylenediamine alone. The use of a modified ion exchange resin prepared from a diamine compound composed of undecanediamine and p-phenylenediamine synergistically enhances the copper ion removal capacity of the modified ion exchange resin, resulting in the prepared modified ion exchange resin exhibiting excellent copper ion removal capacity.

Claims

1. A method for preparing a modified ion exchange resin for removing metal ions as impurities in a plating solution, characterized in that: The following steps are included: Amination reaction step: taking an ion exchange resin and a diamine compound, mixing them, adding a solvent and stirring them evenly, stirring and reacting them at 40-60° C. for 4-6 hours to obtain an aminated ion exchange resin; The cross-linking reaction step comprises adding an aminated ion exchange resin to a formaldehyde aqueous solution, adjusting the pH value to 7 to 9, and stirring the reaction at 50 to 70° C. for 4 to 6 hours to obtain a cross-linked ion exchange resin; and taking the cross-linked ion exchange resin to obtain the modified ion exchange resin for removing impurity metal ions in the plating solution.

2. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 1, wherein: In the amination reaction step, the weight ratio of the ion exchange resin to the diamine compound is 10:2-4.

3. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 2, wherein: In the amination reaction step, the weight ratio of the ion exchange resin to the diamine compound is 10:

3.

4. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 1, wherein: The diamine compound is selected from undecanediamine or p-phenylenediamine.

5. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 1, wherein: The solvent in the amination reaction step is methanol.

6. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 1, wherein: In the cross-linking reaction step, the ratio of the amount of the aminated ion exchange resin to the formaldehyde aqueous solution is 1 kg: 3 to 5 L.

7. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 1, characterized in that: In the cross-linking reaction step, the ratio of the aminated ion exchange resin to the formaldehyde aqueous solution is 1 kg:4 L.

8. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 1, wherein: The mass fraction of formaldehyde in the formaldehyde aqueous solution is 35-40%.

9. The method for preparing a modified ion exchange resin for removing impurity metal ions in a plating solution according to claim 1, wherein: The mass fraction of formaldehyde in the formaldehyde aqueous solution is 37%.

10. The modified ion exchange resin for removing impurity metal ions from plating solution prepared by the preparation method according to any one of claims 1 to 9.

Images